Shampoo composition comprising low viscosity emulsified silicone polymers

ABSTRACT

A shampoo composition including (a) a silicone polymer including (i) one or more quaternary groups; (ii) at least one silicone block comprising greater than 200 siloxane units; (iii) at least one polyalkylene oxide structural unit; and (iv) at least one terminal ester group, and (b) a detersive surfactant. The silicone polymer has a viscosity of up to 100,000 mPa·s. The silicone polymer is a pre-emulsified dispersion with a particle size of less than about 1 micron.

FIELD OF THE INVENTION

Provided is a shampoo composition comprising (1) a silicone polymercontaining quaternary groups and silicone blocks linked to alkyleneoxides (e.g., ethylene oxide and/or propylene oxide), wherein thesilicone polymer has a viscosity of up to 100,000 mPa·s, wherein thesilicone polymer is a pre-emulsified dispersion with a particle size ofless than about 1 micron; and (2) a detersive surfactant.

BACKGROUND OF THE INVENTION

Silicone polymers are strategically important materials in hair care,especially in providing conditioning benefits to hair. Human hairbecomes damaged due to, for example, combing, permanent waves, and/orcoloring the hair. Such damaged hair is often left hydrophilic and/or ina rough condition especially when the hair dries, compared tonon-damaged or less damaged hair. Silicone polymers consisting of blocksof silicones and alkylene oxide (e.g., ethylene oxide and propyleneoxide groups (EO/PO)) linked with amine- and quat-functional groups havebeen used to counteract the hydrophilic nature of damaged hair. Siliconeblocks are responsible for conditioning and lubrication performancewhile amine- and quat-functional groups included in the polymer chainfurther aid deposition during rinsing. In particular, optimumconditioning performance has been observed for silicone blocks ofgreater than 200 D units. However these materials generally have highviscosities as neat materials. In order to achieve the desiredconditioning benefits, these silicone polymers have traditionally beenused in blends with silicone copolyols or other diluents or solvents.

Based on the foregoing, there is a need a shampoo composition whichprovides even greater improved conditioning benefits such as smooth feeland reduced friction on wet hair and dry hair. In addition, there is aneed for a shampoo composition which provides improved conditioningbenefits on damaged hair.

SUMMARY OF THE INVENTION

According to an embodiment of the invention, there is provided a shampoocomposition comprising (a) a silicone polymer comprising: (i) one ormore quaternary groups; (ii) at least one silicone block comprisinggreater than 200 siloxane units; (iii) at least one polyalkylene oxidestructural unit; and (iv) at least one terminal ester group, whereinsaid silicone polymer has a viscosity of up to 100,000 mPa·s, whereinsaid silicone polymer is a pre-emulsified dispersion with a particlesize of less than about 1 micron; and (b) a detersive surfactant.

According to another embodiment of the invention, there is provided amethod of providing improved cleaning and conditioning benefits to hairand/or skin, the method comprising the step of washing said hair and/orskin with a shampoo composition comprising (a) a silicone polymercomprising: (i) one or more quaternary groups; (ii) at least onesilicone block comprising greater than 200 siloxane units; (iii) atleast one polyalkylene oxide structural unit; and (iv) at least oneterminal ester group, wherein said silicone polymer has a viscosity ofup to 100,000 mPa·s; and (b) a detersive surfactant.

These and other features, aspects, and advantages of the invention willbecome evident to those skilled in the art from a reading of thefollowing disclosure.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed that the providedinvention will be better understood from the following description.

In all embodiments of the provided invention, all percentages are byweight of the total composition, unless specifically stated otherwise.All ratios are weight ratios, unless specifically stated otherwise. Thenumber of significant digits conveys neither a limitation on theindicated amounts nor on the accuracy of the measurements. All numericalamounts are understood to be modified by the word “about” unlessotherwise specifically indicated. Unless otherwise indicated, allmeasurements are understood to be made at about 25° C. and at ambientconditions, wherein “ambient conditions” means conditions under aboutone atmosphere of pressure and at about 50% relative humidity. All suchweights as they pertain to listed ingredients are based on the activelevel and do not include carriers or by-products that may be included incommercially available materials, unless otherwise specified.

The term “comprising,” as used herein, means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of.”The processes of the provided invention can comprise, consist of, andconsist essentially of the elements and limitations of the inventiondescribed herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

A. Silicone Polymer Containing Quaternary Groups

The compositions of the present invention comprise a low viscositysilicone polymer having a viscosity up to 100,000 mPa·s. Without beingbound by theory, this low viscosity silicone polymer provides improvedconditioning benefits over conventional silicones because of theaddition of hydrophobic functionalities—quaternary amines, ethyleneoxides/propylene oxides. Compared to previously disclosed silicones withquaternary functionality, these new structures are significantly lowerin viscosity, so that they don't have to be blended with other lowerviscosity diluents and dispersants to allow them to be formulated intoproducts. Low viscosity silicone solvents and diluents can often causeviscosity and stability tradeoffs in shampoo products. The currentinvention eliminates the need for these materials since the siliconepolymer is low enough in viscosity to be added directly or in emulsionform. The improved conditioning benefits include smooth feel, reducedfriction, and prevention of hair damage, while, in some embodiments,eliminating the need for a silicone blend.

Structurally, the silicone polymer is a polyorganosiloxane compoundcomprising one or more quaternary ammonium groups, at least one siliconeblock comprising greater than 200 siloxane units, at least onepolyalkylene oxide structural unit, and at least one terminal estergroup. In one or more embodiments, the silicone block may comprisebetween 300 to 500 siloxane units.

The silicone polymer is present in an amount of from about 0.05% toabout 15%, preferably from about 0.1% to about 10%, more preferably fromabout 0.15% to about 5%, and even more preferably from about 0.2% toabout 4% by weight of the composition.

In a preferred embodiment the polyorganosiloxane compounds according tothe invention have the general formulas (Ia) and (Ib):M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(NR²-A-E-A′-NR²)—Y—]_(k)-M  (Ia)M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(N⁺R² ₂-A-E-A′-N⁺R² ₂)—Y—]_(k)-M  (Ib)wherein:

-   -   m is >0, preferred 0.01 to 100, more preferred 0.1 to 100, even        more preferred 1 to 100, specifically 1 to 50, more specifically        1 to 20, even more specifically 1 to 10,    -   k is 0 or an average value of from >0 to 50, or preferably from        1 to 20, or even more preferably from 1 to 10,    -   M represents a terminal group, comprising terminal ester groups        selected from        -   —OC(O)—Z        -   —OS(O)₂—Z        -   —OS(O₂)O—Z        -   —OP(O)(O—Z)OH        -   —OP(O)(O—Z)₂        -   wherein Z is selected from monovalent organic residues            having up to 40 carbon atoms, optionally comprising one or            more hetero atoms;    -   A and A′ each are independently from each other selected from a        single bond or a divalent organic group having up to 10 carbon        atoms and one or more hetero atoms, and    -   E is a polyalkylene oxide group of the general formula:        —[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)[CH₂CH(C₂H₅)O]_(s)—        -   wherein q=0 to 200, r=0 to 200, s=0 to 200, and q+r+s=1 to            600.    -   R² is selected from hydrogen or R,    -   R is selected from monovalent organic groups having up to 22        carbon atoms and optionally one or more heteroatoms, and wherein        the free valencies at the nitrogen atoms are bound to carbon        atoms,    -   Y is a group of the formula:        —K—S—K— and -A-E-A′- or -A′-E-A-,        -   with S═

-   -   -   wherein R1=C₁-C₂₂-alkyl, C₁-C₂₂-fluoralkyl or aryl; n=200 to            1000, and these can be identical or different if several S            Groups are present in the polyorganosiloxane compound;        -   K is a bivalent or trivalent straight chain, cyclic and/or            branched C₂-C₄₀ hydrocarbon residue which is optionally            interrupted by —O—, —NH—, trivalent N, —NR¹—, —C(O)—,            —C(S)—, and optionally substituted with —OH, wherein R¹ is            defined as above,

    -   T is selected from a divalent organic group having up to 20        carbon atoms and one or more hetero atoms.

The residues K may be identical or different from each other. In the—K—S—K— moiety, the residue K is bound to the silicon atom of theresidue S via a C—Si-bond.

Due to the possible presence of amine groups (—(NR²-A-E-A′-NR²)—) in thepolyorganosiloxane compounds, they may have protonated ammonium groups,resulting from the protonation of such amine groups with organic orinorganic acids. Such compounds are sometimes referred to as acidaddition salts of the polyorganosiloxane compounds according to theinvention.

In a preferred embodiment the molar ratio of the quaternary ammoniumgroups b) and the terminal ester groups c) is less than 100:20, evenmore preferred is less than 100:30 and is most preferred less than100:50. The ratio can be determined by ¹³C-NMR.

In a further embodiment, the polyorganosiloxane composition maycomprise: (A) at least one polyorganosiloxane compound, comprising (i)at least one polyorganosiloxane group, (ii) at least one quaternaryammonium group, (iii) at least one terminal ester group, and (iv) atleast one polyalkylene oxide group (as defined before); and (B) at leastone polyorganosiloxane compound, comprising at least one terminal estergroup, different from compound (A).

In the definition of component (A) it can be referred to the descriptionof the polyorganosiloxane compounds of the invention. Thepolyorganosiloxane compound (B) differs from the polyorganosiloxanecompound (A) preferably in that it does not comprise quaternary ammoniumgroups. Preferred polyorganosiloxane compounds (B) result from thereaction of monofunctional organic acids, in particular carboxylicacids, and polyorganosiloxane containing bisepoxides.

In the polyorganosiloxane compositions according to the invention theweight ratio of compound (A) to compound (B) is preferably less than90:10. Or in other words, the content of component (B) is at least 10weight percent. In a further preferred embodiment of thepolyorganosiloxane compositions according to the invention in compound(A) the molar ratio of the quaternary ammonium groups (ii) and theterminal ester groups (iii) is less than 100:10, even more preferred isless than 100:15 and is most preferred less than 100:20.

The silicone polymer has a viscosity at 20° C. and a shear rate of 0.1s⁻¹ (plate-plate system, plate diameter 40 mm, gap width 0.5 mm) of lessthan 100,000 mPa·s (100 Pa·s). In further embodiments, the viscositiesof the neat silicone polymers may range from 500 to 100,000 mPa·s, orpreferably from 500 to 70,000 mPa·s, or more preferably from 500 to50,000 mPa·s, or even more preferably from 500 to 20,000 mPa·s. Infurther embodiments, the viscosities of the neat polymers may range from500 to 10,000 mPa·s, or preferably 500 to 5000 mPa·s determined at 20°C. and a shear rate of 0.1 s⁻¹.

In addition to the above listed silicone polymers, preferred embodimentsare provided below. For example, in the polyalkylene oxide group E ofthe general formula:—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—[CH₂CH(C₂H₅)O]_(s)—

-   -   wherein the q, r, and s indices may be defined as follows:    -   q=0 to 200, or preferably from 0 to 100, or more preferably from        0 to 50, or even more preferably from 0 to 20,    -   r=0 to 200, or preferably from 0 to 100, or more preferably from        0 to 50, or even more preferably from 0 to 20,    -   s=0 to 200, or preferably from 0 to 100, or more preferably from        0 to 50, or even more preferably from 0 to 20,    -   and q+r+s=1 to 600, or preferably from 1 to 100, or more        preferably from 1 to 50, or even more preferably from 1 to 40.

For polyorganosiloxane structural units with the general formula S:

R¹=C₁-C₂₂-alkyl, C₁-C₂₂-fluoralkyl or aryl; n=from 200 to 1000, orpreferably from 300 to 500, K (in the group —K—S—K—) is preferably abivalent or trivalent straight chain, cyclical or branched C₂-C₂₀hydrocarbon residue which is optionally interrupted by —O—, —NH—,trivalent N, —NR¹—, —C(O)—, —C(S)—, and optionally substituted with —OH.

In specific embodiments, R¹ is C₁-C₁₈ alkyl, C₁-C₁₈ fluoroalkyl andaryl. Furthermore, R¹ is preferably C₁-C₁₈ alkyl, C₁-C₆ fluoroalkyl andaryl. Furthermore, R¹ is more preferably C₁-C₆ alkyl, C₁-C₆ fluoroalkyl,even more preferably C₁-C₄ fluoroalkyl, and phenyl. Most preferably, R¹is methyl, ethyl, trifluoropropyl and phenyl.

As used herein, the term “C₁-C₂₂ alkyl” means that the aliphatichydrocarbon groups possess from 1 to 22 carbon atoms which can bestraight chain or branched. Methyl, ethyl, propyl, n-butyl, pentyl,hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl and1,2,3-trimethyl hexyl moieties serve as examples.

Further as used herein, the term “C₁-C₂₂ fluoroalkyl” means aliphatichydrocarbon compounds with 1 to 22 carbon atoms which can be straightchain or branched and are substituted with at least one fluorine atom.Monofluormethyl, monofluoroethyl, 1,1,1-trifluorethyl, perfluoroethyl,1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl are suitable examples.

Moreover, the term “aryl” means unsubstituted or phenyl substituted onceor several times with OH, F, Cl, CF₃, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₃-C₇cycloalkyl, C₂-C₆ alkenyl or phenyl. Aryl may also mean naphthyl.

For the embodiments of the polyorganosiloxanes, the positive chargesresulting from the ammonium group(s), are neutralized with inorganicanions such as chloride, bromide, hydrogen sulfate, sulfate, or organicanions, like carboxylates deriving from C₁-C₃₀ carboxylic acids, forexample acetate, propionate, octanoate, especially from C₁₀-C₁₈carboxylic acids, for example decanoate, dodecanoate, tetradecanoate,hexadecanoate, octadecanoate and oleate, alkylpolyethercarboxylate,alkylsulphonate, arylsulphonate, alkylarylsulphonate, alkylsulphate,alkylpolyethersulphate, phosphates derived from phosphoric acid monoalkyl/aryl ester and phosphoric acid dialkyl/aryl ester. The propertiesof the polyorganosiloxane compounds can be, inter alia, modified basedupon the selection of acids used.

The quaternary ammonium groups are usually generated by reacting thedi-tertiary amines with an alkylating agents, selected from inparticular di-epoxides (sometimes referred to also as bis-epoxides) inthe presence of mono carboxylic acids and difunctional dihalogen alkylcompounds.

In a preferred embodiment the polyorganosiloxane compounds are of thegeneral formulas (Ia) and (Ib):M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(NR²-A-E-A′-NR²)—Y—]_(k)-M  (Ia)M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(N⁺R² ₂-A-E-A′-N⁺R² ₂)—Y—]_(k)-M  (Ib)

-   -   wherein each group is as defined above; however, the repeating        units are in a statistical arrangement (i.e., not a block-wise        arrangement).

In a further preferred embodiment the polyorganosiloxane compounds maybe also of the general formulas (IIa) or (IIb):M-Y—[—N⁺R₂—Y—]_(m)—[—(NR²-A-E-A′-NR²)—Y—]_(k)-M  (IIa)M-Y—[—N⁺R₂—Y—]_(m)—[—(N⁺R² ₂-A-E-A′-N⁺R² ₂)—Y—]_(k)-M  (IIb)

-   -   wherein each group is as defined above. Also in such formula the        repeating units are usually in a statistical arrangement (i.e        not a block-wise arrangement).    -   wherein, as defined above, M is        -   —OC(O)—Z,        -   —OS(O)₂—Z        -   —OS(O₂)O—Z        -   —OP(O)(O—Z)OH        -   —OP(O)(O—Z)₂    -   Z is a straight chain, cyclic or branched saturated or        unsaturated C₁-C₂₀, or preferably C₂ to C₁₈, or even more        preferably a hydrocarbon radical, which can be interrupted by        one or more —O—, or —C(O)— and substituted with —OH. In a        specific embodiment, M is —OC(O)—Z resulting from normal        carboxylic acids in particular with more than 10 carbon atoms        like for example dodecanoic acid.

In a further embodiment, the molar ratio of thepolyorganosiloxane-containing repeating group —K—S—K— and thepolyalkylene repeating group -A-E-A′- or -A′-E-A- is between 100:1 and1:100, or preferably between 20:1 and 1:20, or more preferably between10:1 and 1:10.

In the group —(N⁺R₂-T-N⁺R₂)—, R may represent a monovalent straightchain, cyclic or branched C₁-C₂₀ hydrocarbon radical, which can beinterrupted by one or more —O—, —C(O)— and can be substituted by —OH, Tmay represent a divalent straight-chain, cyclic, or branched C₁-C₂₀hydrocarbon radical, which can be interrupted by —O—, —C(O)— and can besubstituted by hydroxyl.

The above described polyorganosiloxane compounds comprising quaternaryammonium functions and ester functions may also contain: 1) individualmolecules which contain quaternary ammonium functions and no esterfunctions; 2) molecules which contain quaternary ammonium functions andester functions; and 3) molecules which contain ester functions and noquaternary ammonium functions. While not limited to structure, the abovedescribed polyorganosiloxane compounds comprising quaternary ammoniumfunctions and ester functions are to be understood as mixtures ofmolecules comprising a certain averaged amount and ratio of bothmoieties.

Various monofunctional organic acids may be utilized to yield theesters. Exemplary embodiments include C₁-C₃₀ carboxylic acids, forexample C₂, C₃, C₈ acids, C₁₀-C₁₈ carboxylic acids, for example C₁₂,C₁₄, C₁₆ acids, saturated, unsaturated and hydroxyl functionalized C₁₈acids, alkylpolyethercarboxylic acids, alkylsulphonic acids,arylsulphonic acids, alkylarylsulphonic acids, alkylsulphuric acids,alkylpolyethersulphuric acids, phosphoric acid mono alkyl/aryl estersand phosphoric acid dialkyl/aryl esters.

Further performance improvements can be achieved by pre-dispersing thesilicone polymer in a small particle emulsion (less than 1 micron) priorto adding it to the shampoo base.

The term “emulsion” in this patent application describes any stableemulsion or dispersion of the silicone polymer, separately prepared andused as one of the components of a shampoo composition.

Stable means that the viscosity, particle size, and other importantcharacteristics of the emulsion do not significantly change overreasonable time under exposure to typical temperature, moisture,pressure, shear, light and other environmental conditions that thepre-emulsion is exposed during packing, storage, and transportation

Making the small particle emulsion may require pre-emulsifying thesilicone polymer before their addition to the shampoo composition. Anon-limiting example of a method of making is provided below. All oilsoluble components are mixed in a vessel. Heat may be applied to allowmixture to liquidify. All water soluble components are mixed in aseparate vessel and heated to about same temperature as the oil phase.The oil phase and aqueous phase are mixed under a high shear mixer(example, Turrax mixer by IKA) The particle size of the conditioningactive is in the range of 0.01-5 μm, more preferred 0.05-1 μm, mostpreferred 0.1-0.5 μm. High energy mixing device may be used to achievedesired particle size. High energy mixing device include, but notlimited to Microfluidizer from Microfluidics Corp., Sonolator from SonicCorp., Colloid mill from Sonic Corp.

The emulsifiers which may be selected for each the silicone may beguided by the Hydrophilic-iUpophilic-Balance value (HLB value) ofemulsifiers. Suitable range of HLB value may be 6-16, alternatively8-14. Emulsifiers with a HLB higher than 10 are water soluble.Emulsifiers with low HLB are lipid soluble. To obtain suitable HLBvalue, a mixture of two or more emulsifiers may be used. Suitableemulsifiers include non-ionic, cationic, anionic and amphotericemulsifiers.

The concentration of the emulsifier in the emulsion should be sufficientto provide desired the emulsification of the conditioning active toachieve desired particle size and emulsion stability, and generallyranges from about 0.1 wt %-about 50 wt %, from about 1 wt %-about 30 wt%, from about 2 wt %-about 20 wt %, for example.

The use of a pre-emulsified dispersion of the silicone may presentmultiple advantages including: (i) The small particle size of thesilicones in the emulsion leads to more even deposition and reducesisland-like spotty deposits; and (ii) the more even deposition is morefavorable for providing smoothness for hair/skin surfaces, easiercombing, and enhanced hair volume.

B. Detersive Surfactant

The shampoo composition of the present invention includes a detersivesurfactant, which provides cleaning performance to the composition. Thedetersive surfactant in turn comprises an anionic surfactant, amphotericor zwitterionic surfactants, or mixtures thereof. Various examples anddescriptions of detersive surfactants are set forth in U.S. Pat. No.6,649,155; U.S. Patent Application Publication No. 2008/0317698; andU.S. Patent Application Publication No. 2008/0206355, which areincorporated herein by reference in their entirety.

The concentration of the detersive surfactant component in the shampoocomposition should be sufficient to provide the desired cleaning andlather performance, and generally ranges from about 2 wt % to about 50wt %, from about 5 wt % to about 30 wt %, from about 8 wt % to about 25wt %, or from about 10 wt % to about 20 wt %. Accordingly, the shampoocomposition may comprise a detersive surfactant in an amount of about 5wt %, about 10 wt %, about 12 wt %, about 15 wt %, about 17 wt %, about18 wt %, or about 20 wt %, for example.

Anionic surfactants suitable for use in the compositions are the alkyland alkyl ether sulfates. Other suitable anionic surfactants are thewater-soluble salts of organic, sulfuric acid reaction products. Stillother suitable anionic surfactants are the reaction products of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Other similar anionic surfactants are described in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated hereinby reference in their entirety.

Exemplary anionic surfactants for use in the shampoo composition includeammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laurylsulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In a further embodiment ofthe present invention, the anionic surfactant is sodium lauryl sulfateor sodium laureth sulfate.

Suitable amphoteric or zwitterionic surfactants for use in the shampoocomposition herein include those which are known for use in shampoo orother personal care cleansing. Concentrations of such amphotericsurfactants range from about 0.5 wt % to about 20 wt %, and from about 1wt % to about 10 wt %. Non limiting examples of suitable zwitterionic oramphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and5,106,609, which are incorporated herein by reference in their entirety.

Amphoteric detersive surfactants suitable for use in the shampoocomposition include those surfactants broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight or branched chain and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic group such as carboxy, sulfonate, sulfate,phosphate, or phosphonate. Exemplary amphoteric detersive surfactantsfor use in the present shampoo composition include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the shampoocomposition include those surfactants broadly described as derivativesof aliphatic quaternaryammonium, phosphonium, and sulfonium compounds,in which the aliphatic radicals can be straight or branched chain, andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic group such as carboxy,sulfonate, sulfate, phosphate or phosphonate. In another embodiment,zwitterionics such as betaines are selected.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the compositions aredescribed in McCutcheon's, Emulsifiers and Detergents, 1989 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378, which are incorporated herein byreference in their entirety.

In an embodiment, the composition comprises an anionic surfactant and anon-ionic co-surfactant. In another embodiment the surfactant system isfree, or substantially free of sulfate materials. Suitable sulfate freesurfactants are disclosed in WO publication 2011/120780 and WOpublication 2011/049932.

C. Deposition Polymer

The shampoo composition may also comprise a cationic deposition polymer.These cationic deposition polymers can include at least one of (a) acationic guar polymer, (b) a cationic non-guar galactomannan polymer,(c) a cationic tapioca polymer, (d) a cationic copolymer of acrylamidemonomers and cationic monomers, and/or (e) a synthetic, non-crosslinked,cationic polymer, which may or may not form lyotropic liquid crystalsupon combination with the detersive surfactant (f) a cationic cellulosepolymer. Additionally, the cationic deposition polymer can be a mixtureof deposition polymers.

(1) Cationic Guar Polymers

According to an embodiment of the present invention, the shampoocomposition comprises a cationic guar polymer, which is a cationicallysubstituted galactomannan (guar) gum derivatives. Guar gum for use inpreparing these guar gum derivatives is typically obtained as anaturally occurring material from the seeds of the guar plant. The guarmolecule itself is a straight chain mannan, which is branched at regularintervals with single membered galactose units on alternative mannoseunits. The mannose units are linked to each other by means of β(1-4)glycosidic linkages. The galactose branching arises by way of an α(1-6)linkage. Cationic derivatives of the guar gums are obtained by reactionbetween the hydroxyl groups of the polygalactomannan and reactivequaternary ammonium compounds. The degree of substitution of thecationic groups onto the guar structure must be sufficient to providethe requisite cationic charge density described above.

According to one embodiment, the cationic guar polymer has a weightaverage M.Wt. of less than about 2.5 million g/mol, and has a chargedensity of from about 0.05 meq/g to about 2.5 meq/g. In an embodiment,the cationic guar polymer has a weight average M.Wt. of less than 1.5million g/mol, or from about 150 thousand to about 1.5 million g/mol, orfrom about 200 thousand to about 1.5 million g/mol, or from about 300thousand to about 1.5 million g/mol, or from about 700,000 thousand toabout 1.5 million g/mol. In one embodiment, the cationic guar polymerhas a charge density of from about 0.2 to about 2.2 meq/g, or from about0.3 to about 2.0 meq/g, or from about 0.4 to about 1.8 meq/g; or fromabout 0.5 meq/g to about 1.7 meq/g.

According to one embodiment, the cationic guar polymer has a weightaverage M.Wt. of less than about 1 million g/mol, and has a chargedensity of from about 0.1 meq/g to about 2.5 meq/g. In an embodiment,the cationic guar polymer has a weight average M.Wt. of less than 900thousand g/mol, or from about 150 thousand to about 800 thousand g/mol,or from about 200 thousand to about 700 thousand g/mol, or from about300 thousand to about 700 thousand g/mol, or from about 400 thousand toabout 600 thousand g/mol. from about 150 thousand to about 800 thousandg/mol, or from about 200 thousand to about 700 thousand g/mol, or fromabout 300 thousand to about 700 thousand g/mol, or from about 400thousand to about 600 thousand g/mol. In one embodiment, the cationicguar polymer has a charge density of from about 0.2 to about 2.2 meq/g,or from about 0.3 to about 2.0 meq/g, or from about 0.4 to about 1.8meq/g; or from about 0.5 meq/g to about 1.5 meq/g.

In an embodiment, the composition comprises from about 0.01% to lessthan about 0.7%, or from about 0.04% to about 0.55%, or from about 0.08%to about 0.5%, or from about 0.16% to about 0.5%, or from about 0.2% toabout 0.5%, or from about 0.3% to about 0.5%, or from about 0.4% toabout 0.5%, of cationic guar polymer (a), by total weight of thecomposition.

The cationic guar polymer may be formed from quaternary ammoniumcompounds. In an embodiment, the quaternary ammonium compounds forforming the cationic guar polymer conform to the general formula 1:

wherein where R³, R⁴ and R⁵ are methyl or ethyl groups; R⁶ is either anepoxyalkyl group of the general formula 2:

or R⁶ is a halohydrin group of the general formula 3:

wherein R⁷ is a C₁ to C₃ alkylene; X is chlorine or bromine, and Z is ananion such as Cl—, Br—, I— or HSO₄—.

In an embodiment, the cationic guar polymer conforms to the generalformula 4:

wherein R⁸ is guar gum; and wherein R⁴, R⁵, R⁶ and R⁷ are as definedabove; and wherein Z is a halogen. In an embodiment, the cationic guarpolymer conforms to Formula 5:

Suitable cationic guar polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride. In an embodiment, thecationic guar polymer is a guar hydroxypropyltrimonium chloride.Specific examples of guar hydroxypropyltrimonium chlorides include theJaguar® series commercially available from Rhone-Poulenc Incorporated,for example Jaguar® C-500, commercially available from Rhodia. Jaguar®C-500 has a charge density of 0.8 meq/g and a M.Wt. of 500,000 g/mole.Jaguar® C-17, which has a cationic charge density of about 0.6 meq/g anda M.Wt. of about 2.2 million g/mol and is available from Rhodia Company.Jaguar® C 13S which has a M.Wt. of 2.2 million g/mol and a cationiccharge density of about 0.8 meq/g (available from Rhodia Company). Othersuitable guar hydroxypropyltrimonium chloride are: guarhydroxypropyltrimonium chloride which has a charge density of about 1.1meq/g and a M.Wt. of about 500,000 g/mole is available from ASI, acharge density of about 1.5 meq/g and a M.Wt. of about 500,000 g/mole isavailable from ASI.

Other suitable guar hydroxypropyltrimonium chloride are: Hi-Care 1000,which has a charge density of about 0.7 meq/g and a M.Wt. of about600,000 g/mole and is available from Rhodia; N-Hance 3269 and N-Hance3270, which has a charge density of about 0.7 meq/g and a M.Wt. of about425,000 g/mole and is available from ASI; N-Hance 3196, which has acharge density of about 0.8 and a M. Wt. Of about 1,100,000 g/mole andis available from ASI. AquaCat CG518 has a charge density of about 0.9meq/g and a M.Wt. of about 50,000 g/mole and is available from ASI.BF-13, which is a borate (boron) free guar of charge density of about1.1 meq/g and M. W.t of about 800,000 and BF-17, which is a borate(boron) free guar of charge density of about 1.7 meq/g and M. W.t ofabout 800,000 both available from ASI.

(2) Cationic Non-Guar Galactomannan Polymers

The shampoo compositions of the present invention may comprise agalactomannan polymer derivative having a mannose to galactose ratio ofgreater than 2:1 on a monomer to monomer basis, the galactomannanpolymer derivative selected from the group consisting of a cationicgalactomannan polymer derivative and an amphoteric galactomannan polymerderivative having a net positive charge. As used herein, the term“cationic galactomannan” refers to a galactomannan polymer to which acationic group is added. The term “amphoteric galactomannan” refers to agalactomannan polymer to which a cationic group and an anionic group areadded such that the polymer has a net positive charge.

Galactomannan polymers are present in the endosperm of seeds of theLeguminosae family. Galactomannan polymers are made up of a combinationof mannose monomers and galactose monomers. The galactomannan moleculeis a straight chain mannan branched at regular intervals with singlemembered galactose units on specific mannose units. The mannose unitsare linked to each other by means of β(1-4) glycosidic linkages. Thegalactose branching arises by way of an α(1-6) linkage. The ratio ofmannose monomers to galactose monomers varies according to the speciesof the plant and also is affected by climate. Non Guar Galactomannanpolymer derivatives of the present invention have a ratio of mannose togalactose of greater than 2:1 on a monomer to monomer basis. Suitableratios of mannose to galactose can be greater than about 3:1, and theratio of mannose to galactose can be greater than about 4:1. Analysis ofmannose to galactose ratios is well known in the art and is typicallybased on the measurement of the galactose content.

The gum for use in preparing the non-guar galactomannan polymerderivatives is typically obtained as naturally occurring material suchas seeds or beans from plants. Examples of various non-guargalactomannan polymers include but are not limited to Tara gum (3 partsmannose/1 part galactose), Locust bean or Carob (4 parts mannose/1 partgalactose), and Cassia gum (5 parts mannose/1 part galactose).

In one embodiment of the invention, the non-guar galactomannan polymerderivatives have a M. Wt. from about 1,000 to about 10,000,000, and/orform about 5,000 to about 3,000,000.

The shampoo compositions of the present invention may includegalactomannan polymer derivatives which have a cationic charge densityfrom about 0.5 meq/g to about 7 meq/g. In one embodiment of the presentinvention, the galactomannan polymer derivatives have a cationic chargedensity from about 1 meq/g to about 5 meq/g. The degree of substitutionof the cationic groups onto the galactomannan structure should besufficient to provide the requisite cationic charge density.

In one embodiment of the present invention, the galactomannan polymerderivative is a cationic derivative of the non-guar galactomannanpolymer, which is obtained by reaction between the hydroxyl groups ofthe polygalactomannan polymer and reactive quaternary ammoniumcompounds. Suitable quaternary ammonium compounds for use in forming thecationic galactomannan polymer derivatives include those conforming tothe general formulas 1-5, as defined above.

Cationic non-guar galactomannan polymer derivatives formed from thereagents described above are represented by the general formula 6:

wherein R is the gum. The cationic galactomannan derivative can be a gumhydroxypropyltrimethylammonium chloride, which can be more specificallyrepresented by the general formula 7:

In another embodiment of the invention, the galactomannan polymerderivative is an amphoteric galactomannan polymer derivative having anet positive charge, obtained when the cationic galactomannan polymerderivative further comprises an anionic group.

In one embodiment of the invention the cationic non-guar galactomannanhas a ratio of mannose to galactose is greater than about 4:1, a M. Wt.of about 100,000 to about 500,000, and/or from about 150,000 to about400,000 and a cationic charge density from about 1 meq/g to about 5meq/g, and/or from 2 meq/g to about 4 meq/g and is a derived from acassia plant.

The shampoo compositions of the present invention may comprise at leastabout 0.05% of a galactomannan polymer derivative by weight of thecomposition. In one embodiment of the present invention, the shampoocompositions comprise from about 0.05% to about 2%, by weight of thecomposition, of a galactomannan polymer derivative.

(3) Cationically Modified Starch Polymer

The shampoo compositions of the present invention may comprisewater-soluble cationically modified starch polymers. As used herein, theterm “cationically modified starch” refers to a starch to which acationic group is added prior to degradation of the starch to a smallermolecular weight, or wherein a cationic group is added aftermodification of the starch to achieve a desired molecular weight. Thedefinition of the term “cationically modified starch” also includesamphoterically modified starch. The term “amphoterically modifiedstarch” refers to a starch hydrolysate to which a cationic group and ananionic group are added.

The shampoo compositions of the present invention may comprisecationically modified starch polymers at a range of about 0.01% to about10%, and/or from about 0.05% to about 5%, by weight of the composition.

The cationically modified starch polymers disclosed herein have apercent of bound nitrogen of from about 0.5% to about 4%.

The cationically modified starch polymers for use in the shampoocompositions of the present invention may have a molecular weight fromabout 850,000 to about 15,000,000 and/or from about 900,000 to about5,000,000. As used herein, the term “molecular weight” refers to theweight average molecular weight. The weight average molecular weight maybe measured by gel permeation chromatography (“GPC”) using a Waters 600EHPLC pump and Waters 717 auto-sampler equipped with a PolymerLaboratories PL Gel MIXED-A GPC column (Part Number 1110-6200,600.times.7.5 mm, 20 um) at a column temperature of 55.degree. C. and ata flow rate of 1.0 ml/min (mobile phase consisting of Dimethylsulfoxidewith 0.1% Lithium Bromide), and using a Wyatt DAWN EOS MALLS(multi-angle laser light scattering detector) and Wyatt Optilab DSP(interferometric refractometer) detectors arranged in series (using adn/de of 0.066), all at detector temperatures of 50° C., with a methodcreated by using a Polymer Laboratories narrow dispersed Polysaccharidestandard (Mw=47,300), with an injection volume of 200 μl.

The shampoo compositions of the present invention may includecationically modified starch polymers which have a charge density offrom about 0.2 meq/g to about 5 meq/g, and/or from about 0.2 meq/g toabout 2 meq/g. The chemical modification to obtain such a charge densityincludes, but is not limited to, the addition of amino and/or ammoniumgroups into the starch molecules. Non-limiting examples of theseammonium groups may include substituents such as hydroxypropyltrimmonium chloride, trimethylhydroxypropyl ammonium chloride,dimethylstearylhydroxypropyl ammonium chloride, anddimethyldodecylhydroxypropyl ammonium chloride. See Solarek, D. B.,Cationic Starches in Modified Starches: Properties and Uses, Wurzburg,O. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp 113-125. Thecationic groups may be added to the starch prior to degradation to asmaller molecular weight or the cationic groups may be added after suchmodification.

The cationically modified starch polymers may have a degree ofsubstitution of a cationic group from about 0.2 to about 2.5. As usedherein, the “degree of substitution” of the cationically modified starchpolymers is an average measure of the number of hydroxyl groups on eachanhydroglucose unit which is derivatized by substituent groups. Sinceeach anhydroglucose unit has three potential hydroxyl groups availablefor substitution, the maximum possible degree of substitution is 3. Thedegree of substitution is expressed as the number of moles ofsubstituent groups per mole of anhydroglucose unit, on a molar averagebasis. The degree of substitution may be determined using proton nuclearmagnetic resonance spectroscopy (“.sup.1H NMR”) methods well known inthe art. Suitable .sup.1H NMR techniques include those described in“Observation on NMR Spectra of Starches in Dimethyl Sulfoxide,Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide”, Qin-JiPeng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and“An Approach to the Structural Analysis of Oligosaccharides by NMRSpectroscopy”, J. Howard Bradbury and J. Grant Collins, CarbohydrateResearch, 71, (1979), 15-25.

The source of starch before chemical modification can be chosen from avariety of sources such as tubers, legumes, cereal, and grains.Non-limiting examples of this source starch may include corn starch,wheat starch, rice starch, waxy corn starch, oat starch, cassaya starch,waxy barley, waxy rice starch, glutenous rice starch, sweet rice starch,amioca, potato starch, tapioca starch, oat starch, sago starch, sweetrice, or mixtures thereof.

In one embodiment of the present invention, cationically modified starchpolymers are selected from degraded cationic maize starch, cationictapioca, cationic potato starch, and mixtures thereof. In anotherembodiment, cationically modified starch polymers are cationic cornstarch and cationic tapioca.

The starch, prior to degradation or after modification to a smallermolecular weight, may comprise one or more additional modifications. Forexample, these modifications may include cross-linking, stabilizationreactions, phosphorylations, and hydrolyzations. Stabilization reactionsmay include alkylation and esterification.

The cationically modified starch polymers may be incorporated into thecomposition in the form of hydrolyzed starch (e.g., acid, enzyme, oralkaline degradation), oxidized starch (e.g., peroxide, peracid,hypochlorite, alkaline, or any other oxidizing agent),physically/mechanically degraded starch (e.g., via the thermo-mechanicalenergy input of the processing equipment), or combinations thereof.

An optimal form of the starch may be one which is readily soluble inwater and forms a substantially clear (% Transmittance.gtoreq.80 at 600nm) solution in water. The transparency of the composition is measuredby Ultra-Violet/Visible (UV/VIS) spectrophotometry, which determines theabsorption or transmission of UV/VIS light by a sample, using a GretagMacbeth Colorimeter Color i 5 according to the related instructions. Alight wavelength of 600 nm has been shown to be adequate forcharacterizing the degree of clarity of cosmetic compositions.

Suitable cationically modified starch may be available from known starchsuppliers. Also suitable for use in the present invention is nonionicmodified starch that could be further derivatized to a cationicallymodified starch as is known in the art. Other suitable modified starchstarting materials may be quaternized, as is known in the art, toproduce the cationically modified starch polymer suitable for use in theinvention.

(4) Cationic Copolymer of an Acrylamide Monomer and a Cationic Monomer

According to an embodiment of the present invention, the shampoocomposition may comprise a cationic copolymer of an acrylamide monomerand a cationic monomer, wherein the copolymer has a charge density offrom about 1.0 meq/g to about 3.0 meq/g. In an embodiment, the cationiccopolymer is a synthetic cationic copolymer of acrylamide monomers andcationic monomers.

In an embodiment, the cationic copolymer comprises:

-   -   (i) an acrylamide monomer of the following Formula AM:

-   -   where R⁹ is H or C₁₋₄ alkyl; and R¹⁰ and R¹¹ are independently        selected from the group consisting of H, C₁₋₄ alkyl, CH₂OCH₃,        CH₂OCH₂CH(CH₃)₂, and phenyl, or together are C₃₋₆cycloalkyl; and    -   (ii) a cationic monomer conforming to Formula CM:

where k=1, each of v, v′, and v″ is independently an integer of from 1to 6, w is zero or an integer of from 1 to 10, and X⁻ is an anion.

In an embodiment, cationic monomer conforming to Formula CM and wherek=1, v=3 and w=0, z=1 and X⁻ is Cl⁻ to form the following structure:

The above structure may be referred to as diquat. In another embodiment,the cationic monomer conforms to Formula CM and wherein v′ and v″ areeach 3, v=1, w=1, y=1 and X⁻ is Cl⁻, such as:

The above structure may be referred to as triquat.

In an embodiment, the acrylamide monomer is either acrylamide ormethacrylamide.

In an embodiment, the cationic copolymer (b) is AM:TRIQUAT which is acopolymer of acrylamide and 1,3-Propanediaminium,N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N′,N,N-pentamethyl-,trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ76).AM:TRIQUAT may have a charge density of 1.6 meq/g and a M.Wt. of 1.1million g/mol.

In an alternative embodiment, the cationic copolymer is of an acrylamidemonomer and a cationic monomer, wherein the cationic monomer is selectedfrom the group consisting of: dimethylaminoethyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl(meth)acrylate, dimethylaminomethyl (meth)acrylamide,dimethylaminopropyl (meth)acrylamide; ethylenimine, vinylamine,2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylatechloride, trimethylammonium ethyl (meth)acrylate methyl sulphate,dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl(meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamidochloride, vinylbenzyl trimethyl ammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

In an embodiment, the cationic copolymer comprises a cationic monomerselected from the group consisting of: cationic monomers includetrimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl(meth)acrylate methyl sulphate, dimethylammonium ethyl (meth)acrylatebenzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylatechloride, trimethyl ammonium ethyl (meth)acrylamido chloride, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethylammonium chloride, and mixtures thereof.

In an embodiment, the cationic copolymer is water-soluble. In anembodiment, the cationic copolymer is formed from (1) copolymers of(meth)acrylamide and cationic monomers based on (meth)acrylamide, and/orhydrolysis-stable cationic monomers, (2) terpolymers of(meth)acrylamide, monomers based on cationic (meth)acrylic acid esters,and monomers based on (meth)acrylamide, and/or hydrolysis-stablecationic monomers. Monomers based on cationic (meth)acrylic acid estersmay be cationized esters of the (meth)acrylic acid containing aquaternized N atom. In an embodiment, cationized esters of the(meth)acrylic acid containing a quaternized N atom are quaternizeddialkylaminoalkyl (meth)acrylates with C1 to C3 in the alkyl andalkylene groups. In an embodiment, the cationized esters of the(meth)acrylic acid containing a quaternized N atom are selected from thegroup consisting of: ammonium salts of dimethylaminomethyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl(meth)acrylate; and diethylaminopropyl (meth)acrylate quaternized withmethyl chloride. In an embodiment, the cationized esters of the(meth)acrylic acid containing a quaternized N atom is dimethylaminoethylacrylate, which is quaternized with an alkyl halide, or with methylchloride or benzyl chloride or dimethyl sulfate (ADAME-Quat). In anembodiment, the cationic monomer when based on (meth)acrylamides arequaternized dialkylaminoalkyl (meth)acrylamides with C1 to C3 in thealkyl and alkylene groups, or dimethylaminopropylacrylamide, which isquaternized with an alkyl halide, or methyl chloride or benzyl chlorideor dimethyl sulfate.

In an embodiment, the cationic monomer based on a (meth)acrylamide is aquaternized dialkylaminoalkyl (meth)acrylamide with C1 to C3 in thealkyl and alkylene groups. In an embodiment, the cationic monomer basedon a (meth)acrylamide is dimethylaminopropylacrylamide, which isquaternized with an alkyl halide, especially methyl chloride or benzylchloride or dimethyl sulfate.

In an embodiment, the cationic monomer is a hydrolysis-stable cationicmonomer. Hydrolysis-stable cationic monomers can be, in addition to adialkylaminoalkyl (meth)acrylamide, all monomers that can be regarded asstable to the OECD hydrolysis test. In an embodiment, the cationicmonomer is hydrolysis-stable and the hydrolysis-stable cationic monomeris selected from the group consisting of: diallyldimethylammoniumchloride and water-soluble, cationic styrene derivatives.

In an embodiment, the cationic copolymer is a terpolymer of acrylamide,2-dimethylammoniumethyl (meth)acrylate quaternized with methyl chloride(ADAME-Q) and 3-dimethylammoniumpropyl (meth)acrylamide quaternized withmethyl chloride (DIMAPA-Q). In an embodiment, the cationic copolymer isformed from acrylamide and acrylamidopropyltrimethylammonium chloride,wherein the acrylamidopropyltrimethylammonium chloride has a chargedensity of from about 1.0 meq/g to about 3.0 meq/g.

In an embodiment, the cationic copolymer has a charge density of fromabout 1.1 meq/g to about 2.5 meq/g, or from about 1.1 meq/g to about 2.3meq/g, or from about 1.2 meq/g to about 2.2 meq/g, or from about 1.2meq/g to about 2.1 meq/g, or from about 1.3 meq/g to about 2.0 meq/g, orfrom about 1.3 meq/g to about 1.9 meq/g.

In an embodiment, the cationic copolymer has a M.Wt. from about 100thousand g/mol to about 2 million g/mol, or from about 300 thousandg/mol to about 1.8 million g/mol, or from about 500 thousand g/mol toabout 1.6 million g/mol, or from about 700 thousand g/mol to about 1.4million g/mol, or from about 900 thousand g/mol to about 1.2 milliong/mol.

In an embodiment, the cationic copolymer is atrimethylammoniopropylmethacrylamide chloride-N-Acrylamide copolymer,which is also known as AM:MAPTAC. AM:MAPTAC may have a charge density ofabout 1.3 meq/g and a M.Wt. of about 1.1 million g/mol. In anembodiment, the cationic copolymer is AM:ATPAC. AM:ATPAC may have acharge density of about 1.8 meq/g and a M.Wt. of about 1.1 milliong/mol.

(5) Cationic Synthetic Polymer

According to an embodiment of the present invention, the shampoocomposition may comprise a cationic synthetic polymer that may be formedfrom

i) one or more cationic monomer units, and optionally

ii) one or more monomer units bearing a negative charge, and/or

iii) a nonionic monomer,

wherein the subsequent charge of the copolymer is positive. The ratio ofthe three types of monomers is given by “m”, “p” and “q” where “m” isthe number of cationic monomers, “p” is the number of monomers bearing anegative charge and “q” is the number of nonionic monomers

In one embodiment, the cationic polymers are water soluble ordispersible, non-crosslinked, synthetic cationic polymers having thefollowing structure:

where A, may be one or more of the following cationic moieties:

where @=amido, alkylamido, ester, ether, alkyl or alkylaryl;where Y=C1-C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy;where ψ=C1-C22 alkyl, alkyloxy, alkyl aryl or alkyl arylox;where Z=C1-C22 alkyl, alkyloxy, aryl or aryloxy;where R1=H, C1-C4 linear or branched alkyl;where s=0 or 1, n=0 or ≦1;where T and R7=C1-C22 alkyl; andwhere X—=halogen, hydroxide, alkoxide, sulfate or alkylsulfate.

Where the monomer bearing a negative charge is defined by R2′=H, C1-C4linear or branched alkyl and R3 as:

where D=O, N, or S;where Q=NH₂ or O;where u=1-6;where t=0-1; andwhere J=oxygenated functional group containing the following elements P,S, C.

Where the nonionic monomer is defined by R2″=H, C1-C4 linear or branchedalkyl, R6=linear or branched alkyl, alkyl aryl, aryl oxy, alkyloxy,alkylaryl oxy and β is defined as

where G′ and G′ are, independently of one another, O, S or N—H and L=0or 1.

Examples of cationic monomers include aminoalkyl (meth)acrylates,(meth)aminoalkyl (meth)acrylamides; monomers comprising at least onesecondary, tertiary or quaternary amine function, or a heterocyclicgroup containing a nitrogen atom, vinylamine or ethylenimine;diallyldialkyl ammonium salts; their mixtures, their salts, andmacromonomers deriving from therefrom.

Further examples of cationic monomers include dimethylaminoethyl(meth)acrylate, dimethylaminopropyl (meth)acrylate,ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl(meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine,vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,diallyldimethyl ammonium chloride.

Suitable cationic monomers include those which comprise a quaternaryammonium group of formula —NR₃ ⁺, wherein R, which is identical ordifferent, represents a hydrogen atom, an alkyl group comprising 1 to 10carbon atoms, or a benzyl group, optionally carrying a hydroxyl group,and comprise an anion (counter-ion). Examples of anions are halides suchas chlorides, bromides, sulphates, hydrosulphates, alkylsulphates (forexample comprising 1 to 6 carbon atoms), phosphates, citrates, formates,and acetates.

Suitable cationic monomers include trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride.

Additional suitable cationic monomers include trimethyl ammonium propyl(meth)acrylamido chloride.

Examples of monomers bearing a negative charge include alphaethylenically unsaturated monomers comprising a phosphate or phosphonategroup, alpha ethylenically unsaturated monocarboxylic acids,monoalkylesters of alpha ethylenically unsaturated dicarboxylic acids,monoalkylamides of alpha ethylenically unsaturated dicarboxylic acids,alpha ethylenically unsaturated compounds comprising a sulphonic acidgroup, and salts of alpha ethylenically unsaturated compounds comprisinga sulphonic acid group.

Suitable monomers with a negative charge include acrylic acid,methacrylic acid, vinyl sulphonic acid, salts of vinyl sulfonic acid,vinylbenzene sulphonic acid, salts of vinylbenzene sulphonic acid,alpha-acrylamidomethylpropanesulphonic acid, salts ofalpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl methacrylate,salts of 2-sulphoethyl methacrylate, acrylamido-2-methylpropanesulphonicacid (AMPS), salts of acrylamido-2-methylpropanesulphonic acid, andstyrenesulphonate (SS).

Examples of nonionic monomers include vinyl acetate, amides of alphaethylenically unsaturated carboxylic acids, esters of an alphaethylenically unsaturated monocarboxylic acids with an hydrogenated orfluorinated alcohol, polyethylene oxide (meth)acrylate (i.e.polyethoxylated (meth)acrylic acid), monoalkylesters of alphaethylenically unsaturated dicarboxylic acids, monoalkylamides of alphaethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamineamides, vinyl alcohol, vinyl pyrolidone, and vinyl aromatic compounds.

Suitable nonionic monomers include styrene, acrylamide, methacrylamide,acrylonitrile, methylacrylate, ethylacrylate, n-propylacrylate,n-butylacrylate, methylmethacrylate, ethylmethacrylate,n-propylmethacrylate, n-butylmethacrylate, 2-ethyl-hexyl acrylate,2-ethyl-hexyl methacrylate, 2-hydroxyethylacrylate and2-hydroxyethylmethacrylate.

The anionic counterion (X—) in association with the synthetic cationicpolymers may be any known counterion so long as the polymers remainsoluble or dispersible in water, in the shampoo composition, or in acoacervate phase of the shampoo composition, and so long as thecounterions are physically and chemically compatible with the essentialcomponents of the shampoo composition or do not otherwise unduly impairproduct performance, stability or aesthetics. Non limiting examples ofsuch counterions include halides (e.g., chlorine, fluorine, bromine,iodine), sulfate and methylsulfate.

In one embodiment, the cationic polymer described herein aids inproviding damaged hair, particularly chemically treated hair, with asurrogate hydrophobic F-layer. The microscopically thin F-layer providesnatural weatherproofing, while helping to seal in moisture and preventfurther damage. Chemical treatments damage the hair cuticle and stripaway its protective F-layer. As the F-layer is stripped away, the hairbecomes increasingly hydrophilic. It has been found that when lyotropicliquid crystals are applied to chemically treated hair, the hair becomesmore hydrophobic and more virgin-like, in both look and feel. Withoutbeing limited to any theory, it is believed that the lyotropic liquidcrystal complex creates a hydrophobic layer or film, which coats thehair fibers and protects the hair, much like the natural F-layerprotects the hair. The hydrophobic layer returns the hair to a generallyvirgin-like, healthier state. Lyotropic liquid crystals are formed bycombining the synthetic cationic polymers described herein with theaforementioned anionic detersive surfactant component of the shampoocomposition. The synthetic cationic polymer has a relatively high chargedensity. It should be noted that some synthetic polymers having arelatively high cationic charge density do not form lyotropic liquidcrystals, primarily due to their abnormal linear charge densities. Suchsynthetic cationic polymers are described in WO 94/06403 to Reich et al.The synthetic polymers described herein can be formulated in a stableshampoo composition that provides improved conditioning performance,with respect to damaged hair.

Cationic synthetic polymers that can form lyotropic liquid crystals havea cationic charge density of from about 2 meq/gm to about 7 meq/gm,and/or from about 3 meq/gm to about 7 meq/gm, and/or from about 4 meq/gmto about 7 meq/gm. In some embodiments, the cationic charge density isabout 6.2 meq/gm. The polymers also have a M. Wt. of from about 1,000 toabout 5,000,000, and/or from about 10,000 to about 2,000,000, and/orfrom about 100,000 to about 2,000,000.

In another embodiment of the invention cationic synthetic polymers thatprovide enhanced conditioning and deposition of benefit agents but donot necessarily form lytropic liquid crystals have a cationic chargedensity of from about 0.7 meq/gm to about 7 meq/gm, and/or from about0.8 meq/gm to about 5 meq/gm, and/or from about 1.0 meq/gm to about 3meq/gm. The polymers also have a M. Wt. of from about 1,000 to about5,000,000, from about 10,000 to about 2,000,000, and from about 100,000to about 2,000,000.

The concentration of the cationic polymers ranges about 0.025% to about5%, from about 0.1% to about 3%, and/or from about 0.2% to about 1%, byweight of the shampoo composition.

(6) Cationic Cellulose Polymers

Suitable cationic cellulose polymers may be salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide, referredto in the industry (CTFA) as Polyquaternium 10 and available fromDwo/Amerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KGseries of polymers. Other suitable types of cationic cellulose includethe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide referred to inthe industry (CTFA) as Polyquaternium 24. These materials are availablefrom Dow/Amerchol Corp. under the tradename Polymer LM-200. Othersuitable types of cationic cellulose include the polymeric quaternaryammonium salts of hydroxyethyl cellulose reacted with lauryl dimethylammonium-substituted epoxide and trimethyl ammonium substituted epoxidereferred to in the industry (CTFA) as Polyquaternium 67. These materialsare available from Dow/Amerchol Corp. under the tradename SoftCATPolymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100,Polymer SK-L, Polymer SK-M, Polymer SK-MH, and Polymer SK-H.

In an embodiment, the shampoo composition may comprise a plurality ofcationic conditioning polymers. According to one embodiment, where twocationic conditioning polymers are present, the weight ratio of a firstcationic conditioning polymer to a second cationic conditioning polymeris from about 1000:1 to about 2:1. In an embodiment, the weight ratio ofthe first cationic conditioning polymer to the second cationicconditioning polymer is from about 1000:1 to about 4:1. In anembodiment, weight ratio of the first cationic conditioning polymer tothe second cationic conditioning polymer is from about 800:1 to about4:1, or from about 500:1 to about 4:1, or from about 100:1 to about 5:1,or from about 100:1 to about 6:1, or from about 50:1 to about 6.5:1, orfrom about 50:1 to about 7:1, or from about 50:1 to about 8.3:1, or fromabout 50:1 to about 16.7:1.

D. Carrier

The shampoo compositions can be in the form of pourable liquids (underambient conditions). Such compositions may comprise a carrier, which ispresent at a level of from about 20 wt % to about 95 wt %, or even fromabout 60 wt % to about 85 wt %. The carrier may comprise water, or amiscible mixture of water and organic solvent, and in one aspect maycomprise water with minimal or no significant concentrations of organicsolvent, except as otherwise incidentally incorporated into thecomposition as minor ingredients of other essential or optionalcomponents.

The carrier useful in embodiments of the shampoo compositions of thepresent invention includes water and water solutions of lower alkylalcohols and polyhydric alcohols. The lower alkyl alcohols useful hereinare monohydric alcohols having 1 to 6 carbons, in one aspect, ethanoland isopropanol. Exemplary polyhydric alcohols useful herein includepropylene glycol, hexylene glycol, glycerin, and propane diol.

E. Optional Ingredients

In accordance with embodiments of the present invention, the shampoocomposition may further comprise one or more optional ingredients,including benefit agents Suitable benefit agents include, but are notlimited to conditioning agents, silicone emulsions, anti-dandruffactives, gel networks, chelating agents, and, natural oils such as sunflower oil or castor oil. Additional suitable optional ingredientsinclude but are not limited to perfumes, perfume microcapsules,colorants, particles, anti-microbials, foam busters, anti-static agents,rheology modifiers and thickeners, suspension materials andstructurants, pH adjusting agents and buffers, preservatives,pearlescent agents, solvents, diluents, anti-oxidants, vitamins andcombinations thereof.

Such optional ingredients should be physically and chemically compatiblewith the components of the composition, and should not otherwise undulyimpair product stability, aesthetics, or performance. The CTFA CosmeticIngredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry,and Fragrance Association, Inc., Washington, D.C.) (2004) (hereinafter“CTFA”), describes a wide variety of nonlimiting materials that can beadded to the composition herein.

1. Silicones

The shampoo composition may further comprise one or more siliconeconditioning agents in addition to the silicone quaternary polymersdisclosed in Section A. The additional silicone conditioning agent maycomprise volatile silicone, non-volatile silicone, or combinationsthereof. The concentration of the silicone conditioning agent typicallyranges from about 0.01% to about 10%, by weight of the composition, fromabout 0.1% to about 8%, from about 0.1% to about 5%, and/or from about0.2% to about 3%. Non-limiting examples of suitable siliconeconditioning agents, and optional suspending agents for the silicone,are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646,and U.S. Pat. No. 5,106,609, which descriptions are incorporated hereinby reference. The silicone conditioning agents for use in thecompositions of the present invention can have a viscosity, as measuredat 25° C., from about 20 to about 2,000,000 centistokes (“csk”), fromabout 1,000 to about 1,800,000 csk, from about 50,000 to about 1,500,000csk, and/or from about 100,000 to about 1,500,000 csk.

The dispersed silicone conditioning agent particles typically have avolume average particle diameter ranging from about 0.01 micrometer toabout 50 micrometer. For small particle application to hair, the volumeaverage particle diameters typically range from about 0.01 micrometer toabout 4 micrometer, from about 0.01 micrometer to about 2 micrometer,from about 0.01 micrometer to about 0.5 micrometer. For larger particleapplication to hair, the volume average particle diameters typicallyrange from about 5 micrometer to about 125 micrometer, from about 10micrometer to about 90 micrometer, from about 15 micrometer to about 70micrometer, and/or from about 20 micrometer to about 50 micrometer.

Additional material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989), incorporated herein byreference.

Silicone emulsions suitable for use in the embodiments of the presentinvention include, but are not limited to, emulsions of insolublepolysiloxanes prepared in accordance with the descriptions provided inU.S. Pat. No. 4,476,282 and U.S. Patent Application Publication No.2007/0276087. Accordingly, suitable insoluble polysiloxanes includepolysiloxanes such as alpha, omega hydroxy-terminated polysiloxanes oralpha, omega alkoxy-terminated polysiloxanes having a molecular weightwithin the range from about 50,000 to about 500,000 g/mol. The insolublepolysiloxane can have an average molecular weight within the range fromabout 50,000 to about 500,000 g/mol. For example, the insolublepolysiloxane may have an average molecular weight within the range fromabout 60,000 to about 400,000; from about 75,000 to about 300,000; fromabout 100,000 to about 200,000; or the average molecular weight may beabout 150,000 g/mol. The insoluble polysiloxane can have an averageparticle size within the range from about 30 nm to about 10 micron. Theaverage particle size may be within the range from about 40 nm to about5 micron, from about 50 nm to about 1 micron, from about 75 nm to about500 nm, or about 100 nm, for example.

The average molecular weight of the insoluble polysiloxane, theviscosity of the silicone emulsion, and the size of the particlecomprising the insoluble polysiloxane are determined by methods commonlyused by those skilled in the art, such as the methods disclosed inSmith, A. L. The Analytical Chemistry of Silicones, John Wiley & Sons,Inc.: New York, 1991. For example, the viscosity of the siliconeemulsion can be measured at 30° C. with a Brookfield viscosimeter withspindle 6 at 2.5 rpm. The silicone emulsion may further include anadditional emulsifier together with the anionic surfactant.

Other classes of silicones suitable for use in compositions of thepresent invention include but are not limited to: i) silicone fluids,including but not limited to, silicone oils, which are flowablematerials having viscosity less than about 1,000,000 csk as measured at25° C.; ii) aminosilicones, which contain at least one primary,secondary or tertiary amine; iii) cationic silicones, which contain atleast one quaternary ammonium functional group; iv) silicone gums; whichinclude materials having viscosity greater or equal to 1,000,000 csk asmeasured at 25° C.; v) silicone resins, which include highlycross-linked polymeric siloxane systems; vi) high refractive indexsilicones, having refractive index of at least 1.46, and vii) mixturesthereof.

2. Organic Conditioning Materials

The shampoo composition may also comprise at least one organicconditioning material such as oil or wax, either alone or in combinationwith other conditioning agents, such as the silicones described above.The organic material can be non-polymeric, oligomeric or polymeric. Itmay be in the form of oil or wax and may be added in the formulationneat or in a pre-emulsified form. Some non-limiting examples of organicconditioning materials include, but are not limited to: i) hydrocarbonoils; ii) polyolefins, iii) fatty esters, iv) fluorinated conditioningcompounds, v) fatty alcohols, vi) alkyl glucosides and alkyl glucosidederivatives; vii) quaternary ammonium compounds; viii) polyethyleneglycols and polypropylene glycols having a molecular weight of up toabout 2,000,000 including those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixturesthereof.

3. Emulsifiers

A variety of anionic and nonionic emulsifiers can be used in the shampoocomposition of the present invention. The anionic and nonionicemulsifiers can be either monomeric or polymeric in nature. Monomericexamples include, by way of illustrating and not limitation, alkylethoxylates, alkyl sulfates, soaps, and fatty esters and theirderivatives. Polymeric examples include, by way of illustrating and notlimitation, polyacrylates, polyethylene glycols, and block copolymersand their derivatives. Naturally occurring emulsifiers such as lanolins,lecithin and lignin and their derivatives are also non-limiting examplesof useful emulsifiers.

4. Chelating Agents

The shampoo composition can also comprise a chelant. Suitable chelantsinclude those listed in A E Martell & R M Smith, Critical StabilityConstants, Vol. 1, Plenum Press, New York & London (1974) and A EMartell & R D Hancock, Metal Complexes in Aqueous Solution, PlenumPress, New York & London (1996) both incorporated herein by reference.When related to chelants, the term “salts and derivatives thereof” meansthe salts and derivatives comprising the same functional structure(e.g., same chemical backbone) as the chelant they are referring to andthat have similar or better chelating properties. This term includealkali metal, alkaline earth, ammonium, substituted ammonium (i.e.monoethanolammonium, diethanolammonium, triethanolammonium) salts,esters of chelants having an acidic moiety and mixtures thereof, inparticular all sodium, potassium or ammonium salts. The term“derivatives” also includes “chelating surfactant” compounds, such asthose exemplified in U.S. Pat. No. 5,284,972, and large moleculescomprising one or more chelating groups having the same functionalstructure as the parent chelants, such as polymeric EDDS(ethylenediaminedisuccinic acid) disclosed in U.S. Pat. No. 5,747,440.

Levels of the EDDS chelant in the shampoo compositions can be as low asabout 0.01 wt % or even as high as about 10 wt %, but above the higherlevel (i.e., 10 wt %) formulation and/or human safety concerns mayarise. In an embodiment, the level of the EDDS chelant may be at leastabout 0.05 wt %, at least about 0.1 wt %, at least about 0.25 wt %, atleast about 0.5 wt %, at least about 1 wt %, or at least about 2 wt % byweight of the shampoo composition. Levels above about 4 wt % can be usedbut may not result in additional benefit.

5. Anti-Dandruff Agent

According to an embodiment, the shampoo composition comprises ananti-dandruff active, which may be an anti-dandruff active particulate.The anti-dandruff active can be selected from the group consisting of:pyridinethione salts; azoles, such as an imidazole such as ketoconazole,econazole, climbazole and elubiol; selenium sulphide; coal tar,particulate sulfur; keratolytic agents such as salicylic acid; andmixtures thereof. In an embodiment, the anti-dandruff particulate is apyridinethione salt.

Pyridinethione particulates are suitable particulate anti-dandruffactives. In an embodiment, the anti-dandruff active is a1-hydroxy-2-pyridinethione salt and is in particulate form. In anembodiment, the concentration of pyridinethione anti-dandruffparticulate ranges from about 0.01 wt % to about 5 wt %, or from about0.1 wt % to about 3 wt %, or from about 0.1 wt % to about 2 wt %. In anembodiment, the pyridinethione salts are those formed from heavy metalssuch as zinc, tin, cadmium, magnesium, aluminium and zirconium,generally zinc, typically the zinc salt of 1-hydroxy-2-pyridinethione(known as “zinc pyridinethione” or “ZPT”), commonly1-hydroxy-2-pyridinethione salts in platelet particle form. In anembodiment, the 1-hydroxy-2-pyridinethione salts in platelet particleform have an average particle size of up to about 20 microns, or up toabout 5 microns, or up to about 2.5 microns. Salts formed from othercations, such as sodium, may also be suitable. Pyridinethioneanti-dandruff actives are described, for example, in U.S. Pat. No.2,809,971; U.S. Pat. No. 3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat.No. 3,761,418; U.S. Pat. No. 4,345,080; U.S. Pat. No. 4,323,683; U.S.Pat. No. 4,379,753; and U.S. Pat. No. 4,470,982.

The anti-dandruff active can also be selected from polyvalent metalsalts of pyrithione, the composition further comprises one or moreanti-fungal and/or anti-microbial actives.

Embodiments of the present invention may also comprise a combination ofanti-microbial actives.

In an embodiment, the composition comprises an effective amount of azinc-containing layered material. In an embodiment, the compositioncomprises from about 0.001 wt % to about 10 wt %, or from about 0.01 wt% to about 7 wt %, or from about 0.1 wt % to about 5 wt % of azinc-containing layered material (ZLMs), by total weight of thecomposition.

Many ZLMs occur naturally as minerals. In an embodiment, the ZLM isselected from the group consisting of: hydrozincite (zinc carbonatehydroxide), aurichalcite (zinc copper carbonate hydroxide), rosasite(copper zinc carbonate hydroxide), and mixtures thereof. Relatedminerals that are zinc-containing may also be included in thecomposition. Natural ZLMs can also occur wherein anionic layer speciessuch as clay-type minerals (e.g., phyllosilicates) contain ion-exchangedzinc gallery ions. All of these natural materials can also be obtainedsynthetically or formed in situ in a composition or during a productionprocess.

Another common class of ZLMs, which are often, but not always,synthetic, is layered double hydroxides or hydroxy double salts. In anembodiment, the composition comprises basic zinc carbonate. Basic zinccarbonate, which also may be referred to commercially as “ZincCarbonate” or “Zinc Carbonate Basic” or “Zinc Hydroxy Carbonate”, is asynthetic version consisting of materials similar to naturally occurringhydrozincite.

In embodiments having a zinc-containing layered material and apyrithione or polyvalent metal salt of pyrithione, the ratio ofzinc-containing layered material to pyrithione or a polyvalent metalsalt of pyrithione is from about 5:100 to about 10:1, or from about 2:10to about 5:1, or from about 1:2 to about 3:1.

6. Gel Networks

The shampoo composition may also comprise fatty alcohol gel networks.These gel networks are formed by combining fatty alcohols andsurfactants in the ratio of from about 1:1 to about 40:1, from about 2:1to about 20:1, and/or from about 3:1 to about 10:1. The formation of agel network involves heating a dispersion of the fatty alcohol in waterwith the surfactant to a temperature above the melting point of thefatty alcohol. During the mixing process, the fatty alcohol melts,allowing the surfactant to partition into the fatty alcohol droplets.The surfactant brings water along with it into the fatty alcohol. Thischanges the isotropic fatty alcohol drops into liquid crystalline phasedrops. When the mixture is cooled below the chain melt temperature, theliquid crystal phase is converted into a solid crystalline gel network.The gel network contributes a stabilizing benefit to hair compositions.In addition, they deliver conditioned feel benefits.

The fatty alcohol can be included in the fatty alcohol gel network at alevel by weight of from about 0.05 wt % to about 14 wt %. For example,the fatty alcohol may be present in an amount ranging from about 1 wt %to about 10 wt %, and/or from about 6 wt % to about 8 wt %.

The fatty alcohols useful herein include those having from about 10 toabout 40 carbon atoms, from about 12 to about 22 carbon atoms, fromabout 16 to about 22 carbon atoms, and/or about 16 to about 18 carbonatoms. These fatty alcohols can be straight or branched chain alcoholsand can be saturated or unsaturated. Nonlimiting examples of fattyalcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, andmixtures thereof. Mixtures of cetyl and stearyl alcohol in a ratio offrom about 20:80 to about 80:20 are suitable.

Gel network preparation: A vessel is charged with water and the water isheated to about 74° C. Cetyl alcohol, stearyl alcohol, and SLESsurfactant are added to the heated water. After incorporation, theresulting mixture is passed through a heat exchanger where the mixtureis cooled to about 35° C. Upon cooling, the fatty alcohols andsurfactant crystallized to form a crystalline gel network. Table 3provides the components and their respective amounts for the gel networkcomposition.

TABLE 3 Gel network components Ingredient Wt. % Water 78.27% CetylAlcohol 4.18% Steary Alcohol 7.52% Sodium laureth-3 sulfate (28% Active)10.00% 5-Chloro-2-methyl-4-isothiazolin-3-one, Kathon CG 0.03%

Product Form

The shampoo compositions of the present invention may be presented intypical shampoo formulations. They may be in the form of solutions,dispersion, emulsions, powders, talcs, encapsulated, spheres, spongers,solid dosage forms, foams, and other delivery mechanisms. Thecompositions of the embodiments of the present invention may be hairtonics, leave-on hair products such as treatment, and styling products,rinse-off hair products such as shampoos, and treatment products; andany other form that may be applied to hair.

According to one embodiment, the shampoo compositions may be provided inthe form of a porous, dissolvable solid structure having a percent opencell content of from about 80% to about 100%, such as those disclosed inU.S. Patent Application Publication Nos. 2009/0232873; and 2010/0179083,which are incorporated herein by reference in their entirety.

The shampoo composition can have a viscosity of 4,000 cP to 20,000 cP,or from about 6,000 cP to about 12,000 cP, or from about 8,000 cP toabout 11,000 cP, measured at 26.6° C. with a Brookfield R/S PlusRheometer at 2 s⁻¹. cP means centipoises.

Method of Making

The shampoo compositions are generally prepared by conventional. Suchmethods include mixing of the ingredients in one or more steps to arelatively uniform state, with or without heating, cooling, applicationof vacuum, and the like. The compositions are prepared such as tooptimize stability (physical stability, chemical stability,photostability) and/or delivery of the active materials. The shampoocomposition may be in a single phase or a single product, or the shampoocomposition may be in a separate phases or separate products. If twoproducts are used, the products may be used together, at the same timeor sequentially.

Method of Use

The shampoo compositions of the present invention can be applied to thehair and rinsed off with water.

EXAMPLES

The exemplified compositions can be prepared by conventional formulationand mixing techniques. It will be appreciated that other modificationsof the hair care composition within the skill of those in the hair careformulation art can be undertaken without departing from the spirit andscope of this invention. All parts, percentages, and ratios herein areby weight unless otherwise specified. Some components may come fromsuppliers as dilute solutions. The amount stated reflects the weightpercent of the active material, unless otherwise specified.

Table 1 includes examples of specific structures for the siliconequaternary polymers described in Section A of this application.

TABLE 1 Silicone Silicone Silicone Silicone Silicone QuaternaryQuaternary Quaternary Quaternary Quaternary Variable Polymer A Polymer BPolymer C Polymer D Polymer E M lauric ester lauric ester lauric esterlauric ester lauric ester Y K—S—K K—S—K K—S—K K—S—K K—S—K K CH₂—CHOH—CH₂—CHOH— CH₂—CHOH— CH₂—CHOH— CH₂—CHOH— CH₂—O—C₃H₆ CH₂—O—C₃H₆ CH₂—O—C₃H₆CH₂—O—C₃H₆ CH₂—O—C₃H₆ S PDMS block PDMS block PDMS block PDMS block PDMSblock with 368 with 368 with 368 with 450 with 368 siloxane unitssiloxane units siloxane units siloxane units siloxane units R, R² methylmethyl methyl methyl methyl T C₆H₁₂ C₆H₁₂ C₆H₁₂ C₆H₁₂ C₆H₁₂ A CH₂—COO—CH₂—COO— CH₂—COO— CH₂—COO— CH₂—COO— A′ CO—CH₂ CO—CH₂ CO—CH₂ CO—CH₂CO—CH₂ E Ethylene oxide Ethylene oxide Propylene oxide Propylene oxideEthylene oxide (CH₂—CH₂—O) (CH₂—CH₂—O) (CH₂—CH(CH₃)—O) (CH₂—CH(CH₃)—O)(CH₂—CH₂—O) with average with average with average with average withaverage degree of degree of degree of degree of degree of ethoxylationethoxylation propoxylation propoxylation ethoxylation of 2 of 34 of 3.5of 3.5 of 2 Ratio of silicone 1:1 9:1 9:1 9:1 7:3 blocks:alkylene oxideblocks Total Viscosity 4700 mPa · s 2800 mPa · s 2600 mPa · s. 5400 mPa· s. 6000 mPa · s.

The following examples in Table 2 illustrate embodiments of siliconeemulsions as described in Section A of this Application.

TABLE 2 Silicone Emulsion A B C D E Water q.s. q.s. q.s. q.s. q.s.Sodium Laureth 5.0 — — 5.0 5.0 Sulfate ¹ C11-15 Pareth-5 ² — 1.4 1.0C11-15 Pareth-12 ³ — 2.0 Silicone Quaternary 20.0  Polymer A SiliconeQuaternary 10.0  Polymer B Silicone Quaternary 10.0  Polymer C SiliconeQuaternary 20.0  Polymer D Silicone Quaternary 20.0  Polymer E ¹ SodiumLaureth-1 Sulfate, from Stepan ² Tergitol 15-S-5, from The Dow ChemicalCompany ³ Tergitol 15-S-12, from The Dow Chemical Company

The following examples in Table 3 illustrate embodiments of the presentinvention wherein the silicone polymer is emulsified.

TABLE 3 11 12 13 14 15 16 17 18 19 20 Water q.s. q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s. Sodium Laureth Sulfate ¹ 13.0 12.0 10.5 10.510.5 10.5 10.5 12.0 12.0 12.0 Sodium Lauryl Sulfate ² 1.5 1.5 1.5 1.51.5 1.5 1.5 1.5 1.5 1.5 CMEA ³ — — 0.8 — — — 0.8 — — Cocoamidopropyl 1.71.7 1.0 1.0 1.0 1.0 1.0 1.7 1.7 1.0 Betaine ⁴ Guar Hydroxypropyl 0.3250.3 — — — — — 0.30 — — Trimonium Chloride ⁵ Polyquaternium-10 ⁶ 0.075 —— — — — — — 0.30 — Polyquaternium-6 ⁷ 0.075 — 0.25 — — — — — — —Silicone Emulsion A 5.0 2.5 Silicone Emulsion B 3.75 2.5 SiliconeEmulsion C 2.5 5.0 Silicone Emulsion D 5.0 1.25 Silicone Emulsion E 1.253.75 Glycerine ⁸ 0.5 0.5 — — — — — — — — EGDS ⁹ — — 1.5 — — — 1.5 — — —Trihydroxystearin ¹⁰ 0.1 0.1 — 0.1 0.1 0.1 — 0.1 0.1 0.1 Fragrance, UpUp Up Up Up Up Up Up Up Up preservatives, viscosity to to to to to to toto to to adjustment 3% 3% 3% 3% 3% 3% 3% 3% 3% 3%  ¹ Sodium Laureth-1Sulfate, from Stepan  ² Sodium Lauryl Sulfate, from P&G  ³ Ninol Comf,from Stepan  ⁴ Amphosol HCA-B, from Stepan  ⁵ NHance-3196, from ASI  ⁶Ucare Polymer KG-30M, from The Dow Chemical Company  ⁷ Mirapol 100, fromRhodia Inc.  ⁸ Superol V Glycerine USP, from P&G  ⁹ EGDS pure, fromEvonik ¹⁰ Thixcin R from Elementis

Data

Referring to Table 4, Applicants have surprisingly found thatApplicants' emulsified silicone polymer (QAS 4996) in shampoo showsstatistically significant improved dry conditioning performance whencompared to corresponding emulsified polydimethylsilicone (PDMS)benchmarks.

TABLE 4 Friction Composition Force (g) Shampoo with 1% SiliconeQuaternary Polymer 218.97 A C - milled emulsion Shampoo with 1% PDMS(330,000 cs) - milled 237.63 B emulsion Shampoo with 1% PDMS (5,000cs) - milled 259.74 B emulsion *Compositions sourced from MomentivePerformance Materials

The measurements in Table 4 were taken by measuring the friction force(g) using the Instron Friction Method (IFM).

Instron Friction Method (IFM)

Dry conditioning performance is evaluated by hair friction forcemeasured by an instrument named Instron Tester (Instron Mini 55,Instron, Inc.; Canton, Mass., USA).

-   -   First, a 20 g hair switch is cleaned with tap water running at        about 1.5 gpm at about 100° F.    -   2 ml of Pantene Fine Hair Solutions Flat to Volume Shampoo is        then applied to the hair switch using a syringe, applying half        of the syringe to the front and half of the syringe to the back        of the switch.    -   The Flat to Volume Shampoo is then massaged into the hair using        a milking motion with a thumb on the front of the switch and        fingers on the back for 30 seconds.    -   The switch is then rinsed with tap water running at about 1.5        gpm at about 100° F. for 30 seconds while massaging the hair        using a milking motion with a thumb on the front and fingers on        the back of the switch.    -   The shampoo procedure is repeated.    -   2 ml of the shampoo comprising a conditioning composition is        then applied to the hair using a syringe, applying half of the        syringe to the front and half of the syringe to the back of the        switch.    -   The conditioning composition is then massaged into the hair        using a milking motion with a thumb on the front of the switch        and fingers on the back for 30 seconds.    -   The switch is allowed to rest for 30 seconds.    -   The hair switch is then rinsed with tap water running at about        1.5 gpm at about 100° F. for 30 seconds while massaging the hair        using a milking motion with a thumb on the front and fingers on        the back of the switch.    -   Excess water is removed from the switch by using fingers as a        squeegee, running the fingers down the switch twice.    -   The switch is hung on a cart and taken to a CT/CH room set at        about 70° F. and about 50% room humidity to dry and equilibrate        overnight.    -   The friction force (g) between the hair surface and a foam pad        along the hair is measured using the Instron Mini 55.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A shampoo composition comprising: a) a siliconepolymer comprising: i. one or more quaternary groups; ii. at least onesilicone block comprising greater than 200 siloxane units; iii. at leastone polyalkylene oxide structural unit; and iv. at least one terminalester group  wherein said silicone polymer has a viscosity of up to100,000 mPa·s,  wherein said silicone polymer is a pre-emulsifieddispersion with a particle size of less than about 1 micron, and b) adetersive surfactant.
 2. The shampoo composition of claim 1, whereinsaid silicone block comprises from about 300 to about 600 siloxaneunits.
 3. The shampoo composition of claim 1, wherein said siliconepolymer is present in an amount of from about 0.05% to about 15% byweight of the composition.
 4. The shampoo composition of claim 1,wherein said silicone polymer is present in an amount of from about 0.1%to about 10% by weight of the composition.
 5. The shampoo composition ofclaim 1, wherein said silicone polymer is present in an amount of fromabout 0.15% to about 5% by weight of the composition.
 6. The shampoocomposition of claim 1, wherein said silicone polymer is defined by thefollowing chemical structure:M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(NR²-A-E-A′-NR²)—Y—]_(k)-M  (Ia) wherein:m is an average value of from above 0 to 100 k is an average value offrom above 0 to 50 M represents a terminal group, comprising terminalester groups selected from —OC(O)—Z —OS(O)₂—Z —OS(O₂)O—Z —OP(O)(O—Z)OH—OP(O)(O—Z)₂ wherein Z is selected from monovalent organic residueshaving up to 40 carbon atoms, wherein A and A′ each are independentlyselected from a single bond or a divalent organic group having up to 10carbon atoms and one or more hetero atoms, and E is a polyalkylene oxidegroup of the general formula:—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—[CH₂CH(C₂H₅)O]_(s)— with q=0 to 200,r=0 to 200, s=0 to 200, and q+r+s=1 to 600, R is selected frommonovalent organic groups having up to 22 carbon atoms and optionallyone or more heteroatoms, and wherein the free valencies at the nitrogenatoms are bound to carbon atoms, R² is selected from hydrogen or R, Y isa group of the formula:—K—S—K— and -A-E-A′- or -A′-E-A-, with S═

wherein R¹=C₁-C₂₂-alkyl, C₁-C₂₂-fluoralkyl or aryl, n=200 to 1000, K isa bivalent or trivalent straight chain, cyclic and/or branched C₂-C₄₀hydrocarbon residue which is optionally interrupted by —O—, —NH—,trivalent N, —NR¹—, —C(O)—, —C(S)—, and optionally substituted with —OH,wherein T is selected from a divalent organic group having up to 20carbon atoms and one or more hetero atoms.
 7. The shampoo composition ofclaim 6, wherein the K residues in said —K—S—K— moiety are identical ordifferent, and are bound to the silicon atom of the residue S via aC—Si-bond.
 8. The shampoo composition of claim 1, wherein said siliconepolymer is defined by the following chemical structure:M-Y—[—(N⁺R₂-T-N⁺R₂)—Y—]_(m)—[—(N⁺R² ₂-A-E-A′-N⁺R² ₂)—Y—]_(k)-M  (Ib)wherein: m is an average value of from above 0 to 100 k is an averagevalue of from above 0 to 50 M represents a terminal group, comprisingterminal ester groups selected from —OC(O)—Z —OS(O)₂—Z —OS(O₂)O—Z—OP(O)(O—Z)OH —OP(O)(O—Z)₂ wherein Z is selected from monovalent organicresidues having up to 40 carbon atoms, wherein A and A′ each areindependently selected from a single bond or a divalent organic grouphaving up to 10 carbon atoms and one or more hetero atoms, and E is apolyalkylene oxide group of the general formula:—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—[CH₂CH(C₂H₅)O]_(s)— with q=0 to 200,r=0 to 200, s=0 to 200, and q+r+s=1 to 600, R is selected frommonovalent organic groups having up to 22 carbon atoms and optionallyone or more heteroatoms, and wherein the free valencies at the nitrogenatoms are bound to carbon atoms, R² is selected from hydrogen or R,\ Yis a group of the formula:—K—S—K— and -A-E-A′- or -A′-E-A-, with S═

wherein R¹=C₁-C₂₂-alkyl, C₁-C₂₂-fluoralkyl or aryl, n=200 to 1000, K isa bivalent or trivalent straight chain, cyclic and/or branched C₂-C₄₀hydrocarbon residue which is optionally interrupted by —O—, —NH—,trivalent N, —NR¹—, —C(O)—, —C(S)—, and optionally substituted with —OH,wherein T is selected from a divalent organic group having up to 20carbon atoms and one or more hetero atoms.
 9. The shampoo composition ofclaim 8, wherein the K residues in said —K—S—K— moiety are identical ordifferent, and are bound to the silicon atom of the residue S via aC—Si-bond.
 10. The shampoo composition of claim 8 wherein: m is >0 to10, k is >0 to 10, M is —OC(O)—Z, Z is hydrocarbon chain with 0 to 40carbons q=0-50, r=0-50, q+r is at least 1, s=0, R² is methyl n=300-500.11. The shampoo composition of claim 1, wherein said silicone polymerhas a viscosity of from 500 to 50,000 mPa·s.
 12. The shampoo compositionof claim 1, wherein said silicone polymer has a viscosity of from 500 to5000 mPa·s.
 13. The shampoo composition of claim 1, wherein saiddetersive surfactant is present in an amount of from about 0.5% to about20% by weight of the composition.
 14. A method of providing improvedcleaning and conditioning benefits to hair and/or skin, said methodcomprising the step of washing said hair and/or skin with said shampoocomposition of claim 1.